Process for preparing zein



Patented June 23, 1936 PROCESS FOR PREPARING ZEIN Harry A. Buron, Cambridge, and John Vincent MacDonough, Watertown, Mass., assignors, by mesne assignments, to Arthur D. Little, Inc., a corporation of Massachusetts No Drawing. Application August 7, 1935.

Serial No. 35,102

15 Claims.

This invention relates to zein and to processes for preparing zein; and precipitates the zein in finely divided form as distinguished from a doughy massenabllng it to be washed to yield a purer product than has been commercially posand collected, by Settling, in reservoirs. Water is removed by pressing the gluten in filter presses, and then drying. In the drying operation, the particles of gluten tend to lump together slightly, giving a product consisting generally of small granules which have for example a diameter rangsible heretofore and to have an improved form ing from one to two millimeters down to con- 5 better suited for practical use in the arts. siderably smaller particles.

Processes at present known for recovery of While it is possible to take gluten from an zein from maize ordinarily give a product having earlier stage of the process, it is preferable in a purity of say 85%; purer zein than this has carrying out this invention to take the dried meal. 10 been obtained, but by tedious and expensive op- This meal, being dry, loose and granular, is much erations not well adapted to economic commermore readily penetrated and extracted by so]- cial manufacture. vents than would be the muddy undried gluten.

By the process described in this invention it is Also, there is relatively little water present, hence commercially possible to produce zein of a purity there is less interference with the solvent process 15 greater than 95%, and approaching 100%. Such because of overdilution and necessity for distila product has a wider and more useful applica lation or other effort to separate the water at tion in the arts than has zein of lesser purity. It some stage in the process. The gluten meal maybe manufactured or incorporated into prodprepared as aforesaid will still have associated 2o ucts or substances possessing interesting and with it a small amount of starch, which was that valuable properties. not removed by flotation as hereinbefore de- The dried products of this invention are obsc ibed- HOWEVBI'. if desirech' h remaining tainable in a relatively finely divided form as a starch may be readily removed by suitable op- 7 dry, free-flowing product without resort to long erations such as diastase treatment.

and expensive grinding operation. The parti- For some uses of the zein, the presence of 25 cles, after drying and without any grinding, starch is immaterial, for others it should be rerange in size from small friable aggregates down moved. Therefore, the substantial removal of to minute, almost dustlike particles. 0n acsaid residual starch is optional depending on the count of this friable nature they may be' very use to which the final zein product is to be put.

readily crushed without expensive apparatus or The gluten meal is first extracted by suitable 30 process to form a uniform, very fine granular solvents and in suitable apparatus to remove the powder, which is light in color, dry, and stable, zein, and this extract is then treated by the and without unpleasant odor, and keeps well if process of this invention.

' not exposed to extremes of moisture and warmth. Any suitable extracting apparatus may be used,

The product either before or after any crushing as for example rotary extractors, or a series of 35 operation, is essentially a bulk product, rather percolators. 'I'heoptimum method and appathan a single solid mass or an aggregate of large ratus allow complete penetration of the solvent individual pieces. among and into the particles of gluten meal,

In carrying outthe process of this invention, satisfactory removal of substantially all the avail- 40 to recover zein from maize a relatively dry gluable zein from the meal andconveyance of the 40 ten meal'is the usual starting point for the steps zein solution away from the meal, and conservadescribed herewith. First, however, a brief detion of the solvent. A particularly satisfactory scription of the customary method of making method is that of percolation, in which a series gluten will be given. ofsay four or five extractors filled with gluten The kernels of corn,- freed from the cob, are meal are. subjected to countercurrent extraction 45 steeped in warm water, containing a. small quanwith a suitable zein-solvent. 1 tity of sulphur dioxide as a fermentation pre- The details of this method, as applied to afourventative and a promoter of the softening action. extractor unit, may be briefly as follows. Thus The corn is then passed through mills adapted assume that the extracting process has been in to disintegrate the kernels in such a way that operation long enough to establish the cycle, the 50 the germs may be readily separated, which is extractors being designated A, B, C and D. The done in the next step where the said germs are extraction is countercurrent', so that if the most floated off from a tank of water into which the nearly exhausted meal at the moment is in A, the disintegrated kernels are passed. The kernels, freshest is in D, and the solvent will flow from minus the germ, are then very finely ground, and A towards D. To illustrate-further: nearly ex- 55' bolted to remove the fibrous husks or skin. The hausted meal is in A; fresh solvent is run in and remaining finely ground material, still suspended displaces the solvent already therein, the latter in water, consists primarily of starch and-gluten. quantity of solvent passing into B; similarly from The gluten, being slightly lighter, is floated off, B to C, and C to D, each successive solution containing more zein than the preceding. D con- 60 tains fresh meaLpreferably moistened with a suitable solvent, which may be but "is not necessarily the same as the extracting solvent to promote the action of the main zein-solvent. The next step is to pass heated compressed air or other suitable medium into the meal in A to remove the solvent therein together with the remaining extractable zein which is dissolved in the solvent. This solution in turn passes to B, and so on, while from D there issues the thick syrupy liquid which contains the most zein and which is then processed in accordance with the invention.

The exhausted meal in A is removed and replaced by fresh meal, which is then wet with a solvent as already described in the case of D; fresh solvent is passed into B, and the operation proceeds as already described but with A replacing D, B replacing A, C replacing B, and D replacing C. The solution as issuing from the last extractor in any series is, as already mentioned, thick and syrupy and may contain as high as roughly percent total solids, of which the greater amount (say 85%) is zein.

Alternatively, a rotary extractor may be used, either alone or with a series of such extractors. The operation when using rotaries comprises introducing solvent into the extractor, then introducing gluten meal (thus avoiding the step of wetting fresh meal, as in percolation) agitating, allowing settling, .and filtering ofi the solvent through the settled meal and out through the filter valves at thebottom of the extractor. The extracting is preferably carried out hot, say at a temperature of about 145 F. when aqueous ethanol is used for the solvent. If a series of such extractors is used, the countercurrent principle may be employed; if only one is used, holding tanks should be provided for solutions of different strength, and these solutions are employed successively on new batches of meal in-a manner basically similar to, the countercurrent process. A number of solvents are suitable for use in the above extraction. Some of these are disclosed in U. S. Patent No. 1,966,604. Suitable solvents include most of the alcohols mixed with water, for example, ethanol, normal or isopropanol, tertiary butanol, or the like, in the proportions by volume of substantially 40 to 90% of thealcohol and 60 to 10% water.- Normal butanol saturated with water may be used. Aqueous ethanol is one of the preferred solvents and may consist of 80% ethanol and 20% water. Denatured alcohols may be used, providing they are compatible with the process and not detrimental to the product. The use of more water than this amount in the solvent is less desirable, as there is a tendency for the gluten meal to swell in the presence of such extra water and thereby block the flow of solvent. The

solvent ispreferably used hot as already indicated because it is then more eflective.

The aforesaid zeinextract is then processed as follows to separate the zein from the solvent Tor-distillation and recovery of solvent.

producing a. finely divided precipitate of the min as distinguished from a doughy mass,*=which pre-' cipitate may be easily purified and isin a form readily usable for further processing in the making of many products. This "method involves the control or adjustment of the pH value (hydrogen ion concentration) of the zein solution before precipitating the zein as by diluting the solution. It is known that in usual acid solutions, zein (and accompanying impurities) separates out as a doughy mass, whereas, it has been found that if the solution is strongly alkaline there is a tendency to form a dispersed emulsion; however,

according to the present invention it has been found that if the pH of the solution is adjusted to a point ranging from substantial neutrality (say a pH of 6.5) up to moderate alkalinity, a fiocculent precipitate can be obtained which may bercadily treated and purified. On the alkaline or upper end of the permissible range, the pH value to be employed is largely a question of expediency, for as the alkalinity is increased, the fineness of the product is also increased, thereby lengthening the time necessary for settling or increasing the difliculties of filtration. Actually results have been obtained with a pH ranging up to 12 but for general results the range should not exceed The zein precipitates as a flocculent curdy substance. If desired the pH adjustment may be made by adding the ammonia to the diluting water, insteadof to the zein solution; or it may be added in part to each. Care should be used to add the cold water slowly at first, with continuous stirring, until the curd begins to form; the

rest-of the water is then added more rapidly apparently thus serving to keep the curd from sticking together.

spite of the pH control though this danger is not great at the pH valuespecified.

Other substances than ammonia water maybe used to control the pH value; e. g. sodium or potassium hydroxide or carbonate, or salts of strong bases, and alkalies generally.

The precipitated zein is then allowed to settle; and the supernatant liquor is siphoned off. This liquor maybe treated for recovery of any contained zein, if desired, as by acidifying with for example sulphuric acid, whereupon the zein comes down as a dough. But this step is not essential to the process and may be omitted if desired, the liquor being merelytreated for recovery of solvent, or used in any suitablemanner.

The zein, after removal of the supernatant liquid, is washed by adding cold water and agitating. The zein is again allowed to settle and the water syphoned off. This cold water washing step is repeated numerous times. The wash water from the first two washes may-be saved The precipitate is :too sticky to filter effectively before it is washed. Tofacilitate the removal'of this stickiness, it is preferable to follow four or five of the sold washes with either a warm or a hot Too rapid addition of water may tend to form an emulsion rather thana curd in mately. The zein is allowed to, settle and the warm water syphoned oil. This may be followed with a final cold water wash before the zein is filtered through a light filter cloth and'sucked dry.

The zein cake thus provided may be then broken up very finely and air dried preferably while being agitated. The resulting zein product grinds easily and will have a protein content approximating 97%. Moreover, it will be about 95% soluble, viz. substantially completely soluble in cold 80% ethanol; and of course will be soluble in the hot solvent. This zein product, washed only with cold-water-washes or with cold followed by warm water as aforesaid will be, after drying, the final product, whenever cold-alcohol solubility is a desirable or necessary property of said product. On the other hand, sential, then an even lighter colored zein maybe produced by substituting the warm water by a hot water wash, preferably consisting in boiling the precipitate for a time with water. As before, a final cold washing may be made, but this is optional as the amount of impurities removed is relatively minute. After filtration, the resulting zein cake may be dried by vacuum, air-drying or steam or oven-drying. Where theprecipitate has been boiled, drying even at 212 F. does not injure it. The drying takes place with no appreciable change in particle size, except for occasional loose agglomerates which are easily broken up. This hot water washed zein product is soluble in hot aqueous ethanol, etc. but will have lowered solubility in the cold solvent as com-- pared with the previously described product. The cold solubility of the zein product begins to be lowered when the temperature of the warm water wash (following the cold washes) is to F.; and as said wash water temperature is increased, the solubility of the zein product in the cold solvent becomes less and less, until it is only 66% soluble in cold aqueous ethanol when the precipitate after the cold washes has been boiled in water for, half an hour with vigorous stirring to reduce the tendency to form lumps.

This boiled product (dried and pulverized) compared to the cold and warm water washed product has properties as follows:-It is less odorous, has a lighter color, is much less soluble in cold solvent; and the precipitate from. which the final product is derived, can be dried at 212? F. withoutagglomeration and reversion into a.

horny mass. On the other hand, the .cold and warm waterwashed product (dried and pulverized) has high solubility in the cold solvent; but must be dried at relatively low temperature not exceeding, say F., to avoid agglomeration and reversion into a horny mass.

These zein products will have a purity of 97% to 98% or over. v

It may be desirable to purify the 'zein still further, more nearly approaching 100%. This purication will consist primarily in the removal of traces of residual corn oils 'and fatty acids still associated with the zein; the'bulk' of these were removed with the supernatant liquor; after the zein was first precipitated with pH, control. One may usea solvent for such impurities which has no solvent effect upon zeinin order to accomplish the purification. Such a solvent may be if such solubility is not espersed emulsion when too alkaline.

benzol, carbontetrachloride, ethyl ether, or any a one of several other non-zein solvents. When using such solvents, for example benzol, one may use a trace of acetic acid or the like to neutralize residual alkali left from the controlled pH precipi- 5 tation step and break down fatty acid soaps, the better to dissolve them. The extraction is most efl'ectlve when carried on hot. After the extraction step, the zein is dried, and the solvent recovered or otherwise treated as desired.

The zein produced according to this invention is, as already stated, of particularly high purity. Hence it may be used in the manufacture of more desirable and useful articles or substances than can be made with'the types of zein ordinarily heretofore produced. The zein may be ground to the powder hereinbeforementioned, if desired: such grinding. requires only simple apparatus and little power, as-the zein'granules are crumbled readily.

The zein product of this invention is ready for immediate use in the arts, or it may be stored under proper conditions of relatively low humid-. ity and temperature for long periods of time without deterioration, to be used when desired. The method of preparing zein in accordance with this invention may also be used to purify and improve the form of zein which may have been prepared by other methods. Thus, the doughy or'horny, impure zein prepared by other 30 methods. is purified by the process of this invention by dissolving said zein as far as possible in the hot solvents specified herein, then precipitating with pH control, and washing and drying the precipitate as herein set forth.

While the preferred carrying out of this invention has been described, for purposes of illustration, with considerable detail, it is to be understood that the inventive concept is capable of expression in a variety of ways and that the scope 40 of the invention is not limited to all the details of the disclosure but is to be ascertained from the appended claims in view of the prior art.

What is claimed is:

1. The process of preparing zein which com- 45 prises dissolving the zein in a solvent'comprising water and a suitable organic solvent miscible therewith, adjusting the pH of said solution to a value between approximately 8.5 and 12, and precipitating the zein in a finely divided form by 50 reducing the concentration of the organic solvent.

2. A process as specifiedin claim 1, in which the pH is adjusted'to a range between 6.5 and 9.5.

3. A process as specified in claim 1, in which the pH is adjusted to a range between 7 and 9.

4. The process of preparing zein which comprises dissolving the-rein in a solvent comprising water and a suitable organic solvent miscible therewith, adjusting the pH of said solution to a value between'approximately 6.5 and 12, and 60 cipitating the zein in a finely divided form by largely diluting the solution with water.

5. A process as specified in claim 4, in which such dilution is carried on by adding the water slowly until precipitate is initiated, after whichflfi the water is added more rapidly.

6. The process of preparing zein which comprises dissolving the zein with a suitable water soluble organic solvent, diluting the solution with water and thereby precipitating the zein after ad- 70 itates in finely divided form, as distinguished from a dough when the solution is too acid. or a dis- '1. The process oi claim 6 further characterized by removing the liquor and washing the precipitate with cold water. until filterable.

0. 'I'heproeessotclaimflturthercharacterized .5 by removing the liquor and washing the precipitate with cold iollowed by heated-water washes, until filterable.

9. The process of claim 8 iurther characterized by removing the liquor and washing the precipi- 10 tate with cold water followed by washing it with water heated to between'approximately 130 F. to 140 F.

10. The process of claim 6 further characterized by removing the liquor and washing the precipi-.

16 tate with cold water and then boiling the precipitate withwater.

11., The process oi claim 6 further characterized by removing the liquor and washing the precipitate with cold water followed by washing it with water heated not higher than approximately F. to F., and filtering and drying the precipitate at a temperature not approxi mately F.

' 12. The process of claim 6 further characterized 25 by removing the liquor and washing the precipitate with cold water, then boiling the precipitate with water, and filtering and drying the precipi- CERTIFICATE Patent No. 2,044,769.

awe-res tate in the presence of heat not exceeding a temperature approximating 212 F.

13. The process of preparing zein which comprises dissolving same with a suitable water'soluble organic solvent, adjusting the pH, of said solu- 5 tion to a value between approximately 6.5 and 9.5 and precipitating the zein in finely divided form by adding water to said solution, removing the liquor and washing the precipitate with water,

until filterable.

14. The process of preparing zein which comprises dissolving same with a suitable water sol-'- uble organic solvent, adjusting the pH 01' said solution to a value between approximately 6.5 and 9.5, and precipitating the zein in finely divided 15 form by adding water to said solution, removing the liquor and washing the precipitate with cold followed by heated water washes, until filterable.

15. The process of preparing zein which comprises making a hot solution of the zein with a 20 suitable water soluble organic solvent, cooling said solution and then precipitating the zein by largely diluting the solution with water, atteradjusting its pH to avalue between approximately 6.5 and 9.5, at which the zein precipitates in finely divided 25 form.

HARRY A. HURON.

OF CORRECTION.

June 25, 1936.

HARRY A. BURON, ET AL,

It is hereby certified that error appears in the above numbered patent requiring correction as follows:

Page 4, end of specification, after the signature "HARRY A. BURON" insert the signature of joint inventor, JOHN VIlICEliT MacDONOUGH; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this l5th day of September, A. D, 1936,

,seal) Henry Van A redale ting mm ssi ner r Patents.

'1. The process oi claim 6 further characterized by removing the liquor and washing the precipitate with cold water. until filterable.

0. 'I'heproeessotclaimflturthercharacterized .5 by removing the liquor and washing the precipitate with cold iollowed by heated-water washes, until filterable.

9. The process of claim 8 iurther characterized by removing the liquor and washing the precipi- 10 tate with cold water followed by washing it with water heated to between'approximately 130 F. to 140 F.

10. The process of claim 6 further characterized by removing the liquor and washing the precipi-.

16 tate with cold water and then boiling the precipitate withwater.

11., The process oi claim 6 further characterized by removing the liquor and washing the precipitate with cold water followed by washing it with water heated not higher than approximately F. to F., and filtering and drying the precipitate at a temperature not approxi mately F.

' 12. The process of claim 6 further characterized 25 by removing the liquor and washing the precipitate with cold water, then boiling the precipitate with water, and filtering and drying the precipi- CERTIFICATE Patent No. 2,044,769.

awe-res tate in the presence of heat not exceeding a temperature approximating 212 F.

13. The process of preparing zein which comprises dissolving same with a suitable water'soluble organic solvent, adjusting the pH, of said solu- 5 tion to a value between approximately 6.5 and 9.5 and precipitating the zein in finely divided form by adding water to said solution, removing the liquor and washing the precipitate with water,

until filterable.

14. The process of preparing zein which comprises dissolving same with a suitable water sol-'- uble organic solvent, adjusting the pH 01' said solution to a value between approximately 6.5 and 9.5, and precipitating the zein in finely divided 15 form by adding water to said solution, removing the liquor and washing the precipitate with cold followed by heated water washes, until filterable.

15. The process of preparing zein which comprises making a hot solution of the zein with a 20 suitable water soluble organic solvent, cooling said solution and then precipitating the zein by largely diluting the solution with water, atteradjusting its pH to avalue between approximately 6.5 and 9.5, at which the zein precipitates in finely divided 25 form.

HARRY A. HURON.

OF CORRECTION.

June 25, 1936.

HARRY A. BURON, ET AL,

It is hereby certified that error appears in the above numbered patent requiring correction as follows:

Page 4, end of specification, after the signature "HARRY A. BURON" insert the signature of joint inventor, JOHN VIlICEliT MacDONOUGH; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this l5th day of September, A. D, 1936,

,seal) Henry Van A redale ting mm ssi ner r Patents. 

